CN111138674B - Metal organic framework polymer coated silica gel material, and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a metal organic framework polymer coated silica gel material, a preparation method and application thereof. According to the invention, silica gel microspheres are taken as a matrix, 3-aminopropyltriethoxysilane is bonded to the surfaces of the silica gel microspheres by a chemical bonding method, and a chiral metal organic framework polymer is coated on the surfaces of the silica gel by a self-assembly method, so that a metal organic framework polymer coated silica gel material is formed.
Description
Technical Field
The invention belongs to the technical field of chromatographic separation, and particularly relates to a metal organic framework polymer coated silica gel material, a preparation method thereof and application of the metal organic framework polymer coated silica gel material as a chiral chromatographic stationary phase.
Background
Metal organic framework Materials (MOFs) are receiving attention because of their advantages such as uniform and controllable pore size, large specific surface area, selective adsorption capacity, and good heat resistance. In the field of chromatographic separation, various MOFs materials are used in chromatographic separation modes such as gas chromatography, liquid chromatography, capillary electrochromatography and the like, and show outstanding separation capability in the separation of small molecule compounds.
To meet the separation requirements of chiral compounds, more and more chiral chromatographic stationary phases are being developed and put into the separation industry. In recent years, the research of chiral MOFs materials as the stationary phase of chiral chromatography is also receiving much attention. Theoretically, chiral separation functions can be obtained by fabricating chiral channels or cavities in MOFs. At present, several chiral MOFs materials have been used as chiral stationary phases for gas chromatography and used for separation of chiral compounds in gas chromatography, and a few chiral MOFs materials have been used for resolution of chiral isomers in liquid chromatography.
However, when pure chiral MOFs are used as a stationary phase for liquid chromatography, many problems are often encountered, such as poor packing repeatability, too high column pressure after packing, limited separation efficiency, etc. One important reason is that the shape and size of the particles of chiral MOFs are irregular, which results in that the chromatographic columns packed with MOFs particles tend to have poor reproducibility and it is difficult to obtain long columns with suitable column pressure, so that the enantiomeric separation effect is poor. Therefore, the development of chiral MOFs as a novel chiral stationary phase needs to solve the problems of chromatographic packing uniformity, repeatability and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a metal organic framework polymer coated silica gel material on the basis of the prior art, which takes silica gel microspheres as a substrate, bonds 3-aminopropyltriethoxysilane to the surfaces of the silica gel microspheres by a chemical bonding method, and coats chiral metal organic framework polymers on the surfaces of the silica gel by a self-assembly method, thereby forming the metal organic framework polymer coated silica gel material.
Another object of the present invention is to provide a metal organic framework polymer-coated silica gel material prepared by the above preparation method.
The third purpose of the invention is to provide the application of the metal organic framework polymer coated silica gel material as a chiral chromatographic stationary phase in chromatographic separation.
The technical scheme of the invention is as follows:
a preparation method of a metal organic framework polymer coated silica gel material comprises the following steps:
(1) mixing silica gel microspheres with an alkaline solution, performing ultrasonic treatment, separating the silica gel microspheres, mixing with a dilute acid solution, separating the silica gel microspheres again, washing and drying;
(2) mixing the silica gel microspheres obtained in the step (1) with a solvent, adding 3-aminopropyltriethoxysilane, reacting at 60-150 ℃, filtering, washing and drying after the reaction is finished;
(3) and (3) uniformly mixing the product obtained in the step (2) with a zinc nitrate solution, adding sodium carbonate or a sodium carbonate solution, 4 '-bipyridine or a 4, 4' -bipyridine solution and kaempferic acid or a kaempferic acid solution, fully mixing, reacting at 10-135 ℃, and after the reaction is finished, performing centrifugal separation to obtain the catalyst.
In the step (1), silica gel microspheres with proper size can be selected according to actual requirements, for example, the diameter of the silica gel microspheres is 3-25 μm; preferably 5 to 20 μm; more preferably 8 to 15 μm.
In the step (1), when the silica gel microspheres are mixed with the alkaline solution, the alkaline solution commonly used in the prior art can be adopted, and in order to better implement the method, one or more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution or an ammonia aqueous solution with the pH value of 11-13 can be selected.
In the step (1), the silica gel microspheres are mixed with the alkaline solution and then subjected to ultrasonic treatment at 20-30 ℃, wherein the ultrasonic treatment time can be properly adjusted according to specific conditions, for example, the ultrasonic treatment time is 25-45 minutes.
In a preferable scheme, in the step (1), the silica gel microspheres separated for the first time after ultrasonic treatment are mixed with a dilute acid solution to adjust the pH value of the mixed solution to be 5-6, the silica gel microspheres are separated again, washed with clear water to be 6.5-7.5, and dried for later use.
In order to adjust the pH of the silica gel microspheres, the diluted acid solution may be one or more of the diluted acid solutions commonly used in the prior art, such as, but not limited to, hydrochloric acid, sulfuric acid, formic acid, or acetic acid solution. The concentration of the diluted acid solution can be adjusted according to actual conditions, for example, the concentration of the diluted acid solution is 0.5mol/L to 2 mol/L.
In the step (2), the silica gel microspheres obtained in the step (1) are mixed with an organic solvent, then 3-aminopropyltriethoxysilane is added, the reaction is carried out at the temperature of 60-150 ℃, and after the reaction is finished, the mixture is filtered, washed and dried for standby.
In a preferable scheme, the mass ratio of the silica gel microspheres to the 3-aminopropyltriethoxysilane is 1: 0.5-5, preferably 1: 0.8-3, and more preferably 1: 1.0-2.0.
In the step (2), one or more of benzene, toluene, ethylbenzene or xylene is used as an organic solvent.
In step (2), the washing is thoroughly washed with methanol or acetonitrile.
In a preferable scheme, the mass ratio of the silica gel microspheres to the organic solvent is 1: 5-1: 20, preferably 1: 7-1: 15, and more preferably 1: 10.
Further, in the step (2), the reaction temperature is 100 to 140 ℃.
Further, in the step (2), the reaction time is 18 to 28 hours, preferably 24 hours.
In the step (3), the product obtained in the step (2) is uniformly mixed with a zinc nitrate solution, wherein the concentration of the zinc nitrate solution can be properly adjusted according to the specific conditions of the reaction, for example, the concentration of the zinc nitrate solution is 0.01 to 0.2mol/L, preferably 0.05 to 0.15mol/L, and more preferably 0.1 to 0.15 mol/L.
In the step (3), the volume of the zinc nitrate solution may be determined according to the mass of the silica gel microspheres not mixed with the alkaline solution in the step (1), and in a preferred embodiment, the volume of the zinc nitrate solution required by each gram of the silica gel microspheres is 0.5 to 5mL, preferably 1.5 to 3 mL.
In the step (3), the molar ratio of zinc nitrate to sodium carbonate to the molar ratio of 4, 4' -bipyridine to kaempferic acid is 0.5-5: 0.5-6: 1-7; preferably 0.5-1.5: 0.5-2: 1-3; more preferably 1:1.5:2: 2.
In one scheme, in the step (3), the product obtained in the step (2) is uniformly mixed with a zinc nitrate solution, then a sodium carbonate solution, a 4, 4' -bipyridine solution and a borneol acid solution are added, and after full mixing, reaction is carried out at 10-135 ℃, wherein: the sodium carbonate solution, the 4, 4' -bipyridine solution and the kaempferic acid solution are all aqueous solutions.
The concentration of the sodium carbonate solution is 0.01-0.2 mol/L, preferably 0.05-0.15 mol/L, and more preferably 0.1-0.15 mol/L.
The concentration of the 4, 4' -bipyridine solution is 0.01-0.2 mol/L, preferably 0.05-0.15 mol/L, and more preferably 0.1-0.15 mol/L.
The concentration of the kaempferic acid solution is 0.01-0.2 mol/L, preferably 0.05-0.15 mol/L, and more preferably 0.1-0.15 mol/L.
In a preferable scheme, the volume ratio of the added sodium carbonate solution, the 4, 4' -bipyridine solution and the kaempferol solution to the zinc nitrate solution is 0.5-2: 1-3: 0.5-1.5; preferably 1.5:2:2: 1.
Further, the concentration ratio of the added sodium carbonate solution, 4' -bipyridine solution and kaempferic acid solution to the zinc nitrate solution is 0.8-1.5: 0.8-1.5; preferably 1:1:1: 1.
In a preferable scheme, in the step (3), the reaction temperature is 100-130 ℃.
Further, the reaction time is 32 to 78 hours, preferably 48 hours.
The invention also provides the metal organic framework polymer coated silica gel material prepared by the method.
According to the invention, the silica gel microspheres are used as a matrix, 3-aminopropyltriethoxysilane is bonded to the surfaces of the silica gel microspheres by a chemical bonding method, and the chiral metal organic framework polymer is coated on the surfaces of the silica gel by a self-assembly method, so that the metal organic framework polymer coated silica gel material is formed, and the synthesis method is simple and convenient, and the raw materials are cheap and easy to obtain. The metal organic framework polymer coated silica gel material prepared by the method provided by the invention is used as a composite chiral chromatographic stationary phase, and combines the advantages of high selectivity, large specific surface area and the like of MOFs and the advantages of high mechanical strength, uniform and controllable particle size and the like of silica gel microspheres, so that good chromatographic column filling repeatability and excellent chromatographic separation capability can be obtained, the metal organic framework polymer coated silica gel material can be applied to the field of chromatographic separation, for example, gas chromatographic separation and/or liquid chromatographic separation, aromatic chiral isomers have excellent resolution capability, and the metal organic framework polymer coated silica gel material is particularly used as a chiral chromatographic stationary phase in the separation of chiral isomer 1- (1-naphthyl) ethanol.
By adopting the technical scheme of the invention, the advantages are as follows:
(1) the invention provides a preparation method of MOFs coated silica gel composite chiral chromatographic stationary phase for chiral isomer resolution in liquid chromatography, which has simple preparation scheme and cheap and easily-obtained raw materials.
(2) The composite chiral chromatographic stationary phase prepared by the invention takes the silica gel microspheres as the matrix, so the material has the advantages of uniform and controllable particle size, high mechanical strength and the like, thereby being capable of obtaining good chromatographic column filling repeatability and excellent chromatographic separation capability.
(3) The stationary phase prepared by the invention takes the chiral MOFs material as the chiral selector, so the material has the advantages of large specific surface area, stable physical structure and the like, thereby improving the separation capability of the chromatographic column and prolonging the service life.
Drawings
FIG. 1 is a scanning electron micrograph of a metal organic framework polymer-coated silica gel material prepared according to example 1;
FIG. 2 is a graph showing the results of using the metal organic framework polymer-coated silica gel material prepared in example 1 as a chiral stationary phase for chromatographic separation.
Detailed Description
The metal organic framework polymer-coated silica gel material of the present invention is further illustrated by the following examples in combination with the drawings, but the present invention is not limited by these examples.
Example 1
According to the following steps, synthesizing MOFs coated silica gel composite chiral chromatography stationary phase, and using the MOFs coated silica gel composite chiral chromatography stationary phase for the resolution of chiral enantiomers in liquid chromatography, wherein the specific steps are as follows:
(1) 10g of silica gel microspheres (10 μm,
) Placing the mixture into a clean reaction container, adding NaOH solution (with the pH value of 13), carrying out ultrasonic treatment for 30 minutes at the temperature of 20-30 ℃, carrying out suction filtration, separating out the silica gel microspheres, and then mixing the silica gel microspheres with dilute hydrochloric acid to adjust the pH value to 5-6; separating the silica gel microspheres again, washing the silica gel microspheres with clear water until the pH value is 6.5-7.5, and drying the silica gel microspheres;
(2) placing the treated silica gel microspheres into a clean reaction container with a reflux device, adding 100mL of toluene, then adding 12g of 3-aminopropyltriethoxysilane, heating to 110 ℃ and reacting for 24 hours;
(3) cleaning and filtering the product obtained in the step (2), fully cleaning the product with methanol, drying the product, placing the product into a clean reaction container with a reflux device, adding 20mL of zinc nitrate solution (0.1mol/L), fully and uniformly stirring the mixture, adding 30mL of sodium carbonate solution (0.1mol/L), 40mL of 4, 4' -bipyridyl solution (0.1mol/L) and 40mL of bornanedioic acid solution (0.1mol/L), fully mixing the mixture, and placing the mixture at 120 ℃ for reacting for 48 hours;
(4) and (3) carrying out differential centrifugal separation on the obtained product to obtain the metal organic framework polymer coated silica gel composite chiral chromatographic stationary phase, wherein a scanning electron microscope photo is shown in figure 1.
(5) After the obtained material is fully dispersed by using isopropanol-methanol solution (1: 4), a chromatographic column with the size of 4.6mm multiplied by 250mm is filled under the condition of 60MPa, and the material is used for chiral isomer purification experiments;
(6) using n-hexane-dichloromethane (65:35) as mobile phase, flow rate 1mL/min, ultraviolet detection wavelength 210nm, column temperature 30 deg.C for resolving chiral isomer of 1- (1-naphthyl) -ethanol, and the result is shown in figure 2.
Example 2
According to the following steps, synthesizing MOFs coated silica gel composite chiral chromatography stationary phase, and using the MOFs coated silica gel composite chiral chromatography stationary phase for the resolution of chiral enantiomers in liquid chromatography, wherein the specific steps are as follows:
(1) 10g of silica gel microspheres (12 μm,
) Placing the mixture into a clean reaction container, adding a potassium hydroxide solution (pH is 13), carrying out ultrasonic treatment for 30 minutes at the temperature of 20-30 ℃, carrying out suction filtration, separating out the silica gel microspheres, and then mixing the silica gel microspheres with acetic acid to adjust the pH value to 5-6; separating the silica gel microspheres again, washing the silica gel microspheres with clear water until the pH value is 6.5-7.5, and drying the silica gel microspheres;
(2) placing the treated silica gel microspheres in a clean reaction container with a reflux device, adding 120mL of ethylbenzene, then adding 20g of 3-aminopropyltriethoxysilane, heating to 137 ℃ and reacting for 24 hours;
(3) cleaning and filtering the product obtained in the step (2), fully cleaning the product with methanol, drying the product, placing the product into a clean reaction container with a reflux device, adding 25mL of zinc nitrate solution (0.15mol/L), fully and uniformly stirring the mixture, adding 37.5mL of sodium carbonate solution (0.15mol/L), 50mL of 4, 4' -bipyridyl solution (0.15mol/L) and 50mL of kaempferic acid solution (0.15mol/L), fully mixing the mixture, and placing the mixture at 100 ℃ for reacting for 48 hours;
(4) and (3) carrying out differential centrifugal separation on the obtained product to obtain the metal organic framework polymer coated silica gel composite chiral chromatographic stationary phase.
(5) After the obtained material is fully dispersed by using isopropanol-methanol solution (1: 4), a chromatographic column with the size of 4.6mm multiplied by 250mm is filled under the condition of 60MPa, and the material is used for chiral isomer purification experiments;
(6) the resolution of the chiral isomer of 1- (1-naphthyl) -ethanol was carried out using n-hexane-dichloromethane (65:35) as the mobile phase at a flow rate of 1mL/min, an ultraviolet detection wavelength of 210nm, and a column temperature of 30 ℃ and the results were similar to those in FIG. 2.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: modifications of the technical solutions described in the foregoing embodiments are still possible, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (19)
1. A preparation method of a metal organic framework polymer coated silica gel material is characterized by comprising the following steps:
(1) mixing silica gel microspheres with an alkaline solution, performing ultrasonic treatment for 25-45 minutes at 20-30 ℃, separating the silica gel microspheres, mixing with a dilute acid solution, adjusting the pH value to 5-6, separating the silica gel microspheres again, washing with clear water until the pH value is 6.5-7.5, and drying;
(2) mixing the silica gel microspheres obtained in the step (1) with an organic solvent, adding 3-aminopropyltriethoxysilane, reacting at 100-140 ℃, filtering, washing and drying after the reaction is finished; the mass ratio of the silica gel microspheres to the 3-aminopropyltriethoxysilane is 1: 0.5-5;
(3) uniformly mixing the product obtained in the step (2) with a zinc nitrate solution, adding sodium carbonate or a sodium carbonate solution, 4 '-bipyridine or a 4, 4' -bipyridine solution and kaempferic acid or a kaempferic acid solution, fully mixing, reacting at 100-130 ℃, and after the reaction is finished, performing centrifugal separation to obtain the product; the molar ratio of the zinc nitrate to the sodium carbonate to the 4, 4' -bipyridine to the borneol diacid is 0.5-5: 0.5-6: 1-7.
2. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the silica gel microspheres to the 3-aminopropyltriethoxysilane is 1: 0.8-3.
3. The preparation method according to claim 2, wherein in the step (2), the mass ratio of the silica gel microspheres to the 3-aminopropyltriethoxysilane is 1: 1.0-2.0.
4. The method according to claim 1, wherein in the step (2), the reaction time is 18 to 28 hours.
5. The preparation method according to claim 1, wherein in the step (3), the concentration of the zinc nitrate solution is 0.01 to 0.2 mol/L; the volume of the zinc nitrate solution required by each gram of the silica gel microspheres is 0.5-5 mL.
6. The preparation method according to claim 5, wherein in the step (3), the concentration of the zinc nitrate solution is 0.05 to 0.15 mol/L; the volume of the zinc nitrate solution required by each gram of the silica gel microspheres is 1.5-3 mL.
7. The method according to claim 6, wherein in the step (3), the concentration of the zinc nitrate solution is 0.1 to 0.15 mol/L.
8. The method according to claim 1, wherein in the step (3), the molar ratio of the zinc nitrate to the sodium carbonate, the 4, 4' -bipyridine and the borneol diacid is 0.5-1.5: 0.5-2: 1-3.
9. The method according to claim 8, wherein in the step (3), the molar ratio of the zinc nitrate to the sodium carbonate, the 4, 4' -bipyridine and the borneol diacid is 1:1.5:2: 2.
10. The preparation method according to claim 1, wherein in the step (1), the silica gel microspheres have a diameter of 3 to 25 μm; the alkaline solution is one or more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution or an ammonia aqueous solution with the pH value of 11-13; the dilute acid solution is one or more of hydrochloric acid, sulfuric acid, formic acid or acetic acid solution.
11. The method according to claim 10, wherein in the step (1), the silica gel microspheres have a diameter of 5 to 20 μm.
12. The method according to claim 11, wherein in the step (1), the silica gel microspheres have a diameter of 8 to 15 μm.
13. The preparation method according to claim 1, wherein in the step (2), the organic solvent is one or more of benzene, toluene, ethylbenzene or xylene; the mass ratio of the silica gel microspheres to the organic solvent is 1: 5-1: 20.
14. The production method according to claim 13, wherein in the step (2), the organic solvent is toluene or ethylbenzene; the mass ratio of the silica gel microspheres to the organic solvent is 1: 7-1: 15.
15. The production method according to claim 14, wherein in the step (2), the mass ratio of the silica gel microspheres to the organic solvent is 1: 10.
16. The metal-organic framework polymer-coated silica gel material prepared by the preparation method of any one of claims 1 to 15.
17. Use of a metal organic framework polymer-coated silica gel material according to claim 16 as a stationary phase for chiral chromatography in chromatographic separations.
18. The use according to claim 17, wherein the metal organic framework polymer-coated silica gel material is used as a stationary phase for chiral chromatography in gas chromatography and/or liquid chromatography.
19. The use according to claim 18, wherein the metal-organic framework polymer-coated silica gel material is used as a stationary phase for chiral chromatography in the separation of the chiral isomer 1- (1-naphthyl) ethanol.
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| PCT/CN2020/127114 WO2021129192A1 (en) | 2019-12-27 | 2020-11-06 | Silica gel material coated with metal-organic framework polymer, preparation method therefor and use thereof |
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| CN111138674B (en) * | 2019-12-27 | 2021-09-21 | 江苏阿尔法药业股份有限公司 | Metal organic framework polymer coated silica gel material, and preparation method and application thereof |
| CN112774636A (en) * | 2020-12-30 | 2021-05-11 | 张磊 | Chiral covalent organic framework bonded silicon sphere chromatographic stationary phase, preparation and application thereof |
| CN115184504A (en) * | 2022-07-22 | 2022-10-14 | 陕西中烟工业有限责任公司 | Preparation method of ZIF-8 modified monolithic column and extraction of polycyclic aromatic hydrocarbon in tobacco leaves |
| CN115282928B (en) * | 2022-08-04 | 2023-08-15 | 杭州佳嘉乐生物技术有限公司 | Novel separation medium and application thereof |
| CN116196886A (en) * | 2023-02-28 | 2023-06-02 | 金华市计量质量科学研究院 | Manufacturing method and application of three-dimensional cage-shaped structure chromatographic packing for high performance liquid chromatography |
| CN116272920B (en) * | 2023-03-10 | 2024-05-03 | 西南医科大学 | Triazine covalent organic framework modified silicon sphere novel stationary phase high performance liquid chromatography packing and preparation method and application thereof |
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| CN106166482A (en) * | 2016-07-07 | 2016-11-30 | 安庆师范大学 | The preparation and application of novel chiral MOF skeleton chromatographic column |
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